CN113463108A - Au @ PtCo/CNT catalyst and preparation method and application thereof - Google Patents

Au @ PtCo/CNT catalyst and preparation method and application thereof Download PDF

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Publication number
CN113463108A
CN113463108A CN202110657066.8A CN202110657066A CN113463108A CN 113463108 A CN113463108 A CN 113463108A CN 202110657066 A CN202110657066 A CN 202110657066A CN 113463108 A CN113463108 A CN 113463108A
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ptco
catalyst
cnt
cnt catalyst
source
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杨玺
甘团杰
武建平
廖卫平
晏梦璇
余郁
刘石
刘志刚
杨毅
刘海源
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Guangdong Power Grid Co Ltd
Jiangmen Power Supply Bureau of Guangdong Power Grid Co Ltd
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Guangdong Power Grid Co Ltd
Jiangmen Power Supply Bureau of Guangdong Power Grid Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • C25B1/01—Products
    • C25B1/02—Hydrogen or oxygen
    • C25B1/04—Hydrogen or oxygen by electrolysis of water
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
    • C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/097—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds comprising two or more noble metals or noble metal alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention relates to the technical field of catalysts, and particularly relates to an Au @ PtCo/CNT catalyst as well as a preparation method and application thereof. The invention discloses an Au @ PtCo/CNT catalyst, wherein the existence of Au in the catalyst can improve the stability of a platinum-based catalyst; the monoatomic Co is regulated and controlled through the tensile stress of Au, and the electronic environment around Pt is further improved, so that the catalytic performance of the catalyst is enhanced; the addition of the carbon nano tube greatly improves the specific surface area of the catalyst and increases the number of active sites. According to experimental data, the Au @ PtCo/CNT catalyst provided by the application has the advantages of good stability, good hydrogen evolution reaction performance and high hydrogen evolution reaction speed.

Description

Au @ PtCo/CNT catalyst and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalysts, and particularly relates to an Au @ PtCo/CNT catalyst as well as a preparation method and application thereof.
Background
Currently, Pt catalysts have good Hydrogen Evolution Reaction (HER) performance on the cathode side of fuel cells, but since intermediate products (such as CO and-OH) generated during the reaction cause Pt catalysts to be poisoned, resulting in a decrease in catalytic activity and stability, the presence of Au can improve the stability of platinum-based catalysts because Au is more stable under electrochemical operating conditions.
Meanwhile, the noble metal catalyst has high cost and insufficient content of Au and Pt, so the quality activity of the noble metal catalyst needs to be further improved.
Disclosure of Invention
In view of the above, the invention provides an Au @ PtCo/CNT catalyst, and a preparation method and application thereof.
The specific technical scheme is as follows:
the invention provides an Au @ PtCo/CNT catalyst, which comprises: a carbon nanotube and an Au @ PtCo alloy supported on the carbon nanotube;
the Au @ PtCo alloy is of a core-shell structure, wherein a shell layer is the PtCo alloy, and a core layer is Au. In the invention, the existence of Au in the Au @ PtCo/CNT catalyst can improve the stability of the platinum-based catalyst; the monoatomic Co is regulated and controlled through the tensile stress of Au, and the electronic environment around Pt is further improved, so that the catalytic performance of the catalyst is enhanced; the addition of the carbon nano tube greatly improves the specific surface area of the catalyst and increases the number of active sites. The precious metal shell layer of the Au @ PtCo alloy with the core-shell structure is beneficial to realizing high utilization efficiency of the catalyst, and the catalytic activity can be finely adjusted by establishing core-shell interface strain through changing the bonding strength between the catalyst and reaction molecules, so that the generation of intermediates is reduced.
In the invention, the particle size of the Au @ PtCo alloy is 5-40nm, and preferably 10-20 nm.
In the invention, the thickness of the shell layer is 7-9nm, and the particle size of the core layer is 6-5 nm.
In the invention, the carbon nano tube is a multi-wall carbon nano tube;
the width of the multi-wall carbon nano tube is 16-20nm, and the length of the multi-wall carbon nano tube is 5-6 mu m.
In the invention, the mass contents of Au, Pt, Co and CNT in the Au @ PtCo/CNT catalyst are respectively 5-10%, 10-15%, 0.5-1.5% and 70-90%.
The invention also provides a preparation method of the Au @ PtCo/CNT catalyst, which comprises the following steps:
step 1: mixing a gold source solution and a surfactant solution, adding a carbon nano tube for mixing, and adding a first reducing agent for reaction;
step 2: and (2) adding a cobalt source solution and a platinum source solution into the reaction solution obtained in the step (1), and then adding a second reducing agent to react to obtain the Au @ PtCo/CNT catalyst.
The Au @ PtCo/CNT catalyst is synthesized by a one-pot method, no organic solvent is used in the synthesis process, the dispersion of nanoparticles is good, and the synthesis process is simple, safe and nontoxic; in the preparation process of the invention, the carbon nano tube is added before the gold core is formed, so that the metal nano particles with high dispersion and small size can be formed. In addition, the preparation method also solves the problem of agglomeration in the reduction process of metal ions in the aqueous solution, and simultaneously avoids the problems of complex reaction and blockage of catalytic activity due to the coating of a surfactant in the oil solution.
The step 1 of the invention specifically comprises the following steps: uniformly mixing the gold source solution and the surface active solution, adding the carbon nano tube, carrying out ultrasonic treatment, and adding a first reducing agent to react under the ice bath condition;
the gold source is HAuCl4·3H2O、NaAuCl4·2H2O、NaAuCl4·2H2O and Au2Cl6One or more than two of the above;
the concentration of the gold source solution is 0.05-0.15mol ml-1；
The surfactant is cetyl trimethyl ammonium bromide and/or cetyl trimethyl ammonium chloride; the use of the surfactant of the invention enables the nanoparticles to be more easily formed without agglomeration;
the molar ratio of the surfactant to the gold source is (5: 1) to (10: 1), preferably 15: 2;
the ultrasonic treatment rate is 8000-;
the first reducing agent is sodium borohydride;
the molar ratio of the first reducing agent to the gold source is (1: 1) - (3: 1), preferably 2: 1;
the reaction is carried out under the condition of ice bath, the temperature of the reaction is 0-10 ℃, and the time is 20-40 minutes.
In step 2 of the invention, the cobalt source is CoCl2·6H2O and/or Co (NO)3)2·6H2O；
The platinum source is H2PtCl6·6H2O and/or PtCl4；
The concentration of the platinum source solution is 0.01-0.05mol/L, preferably 0.0265mol/L, and the concentration of the cobalt source solution is 0.05-0.1mol/L, preferably 0.0795 mol/L;
the second reducing agent is one or more than two of L-ascorbic acid, sodium citrate and ferric chloride, and preferably L-ascorbic acid and sodium citrate; the second reducing agent can perform dealloying in the reduction process, so that trace Co is reduced into the crystal lattice of Pt to form PtCo alloy; sodium citrate in the second reducing agent can also be used as a surfactant
The molar ratio of the second reducing agent to the platinum source is (1: 1) to (3: 1), preferably 2: 1;
the reaction temperature is 95-105 ℃ and the reaction time is 2-4 hours, and the reaction is preferably carried out at 100 ℃ for 3 hours.
In the present invention, the molar ratio of the gold source, the platinum source, and the cobalt source is (1: 3: 5) to (1: 1: 1), and preferably 2: 3: 9;
the mass ratio of the gold source, the cobalt source, the platinum source and the carbon nanotube is (1: 5: 3: 7) to (1: 1: 1: 3), and preferably 1: 3: 2: 5.
the reaction solvent in step 1 and step 2 of the invention is deionized water.
The invention also provides the application of the Au @ PtCo/CNT catalyst or the Au @ PtCo/CNT catalyst prepared by the preparation method in hydrogen evolution reaction.
In the present invention, the Au @ PtCo/CNT catalyst is used in PEM hydrogen fuel cells.
The application of the Au @ PtCo/CNT catalyst in the hydrogen evolution reaction comprises the following steps:
dropwise adding catalyst ink on a glassy carbon electrode polished by alumina powder to serve as a working electrode, taking graphite as a counter electrode and an Ag/AgCl electrode as a reference electrode, constructing a three-electrode system, and carrying out electrocatalytic reaction in an alkaline solution to precipitate hydrogen;
in the present invention, the alkaline solution is preferably a potassium hydroxide solution; the concentration of the alkaline solution is 0.5-1.5M, and preferably 1M; the voltage of the electrocatalytic reaction is-0.7V to-1.5V, and the time of the electrocatalytic reaction is 5-7 minutes.
The preparation steps of the catalyst ink are as follows: the Au @ PtCo/CNT catalyst was dispersed in a mixed solution of isopropanol, deionized water and Nafion.
In the invention, in the mixed solution, the volume ratio of isopropanol, deionized water and Nafion is 1: 1: 0.1; the concentration of the Au @ PtCo/CNT catalyst in the mixed solution is 1-10 mg/mL, and preferably 5 mg/mL.
According to the technical scheme, the invention has the following advantages:
the existence of Au in the Au @ PtCo/CNT catalyst provided by the invention can improve the stability of the platinum-based catalyst; the monoatomic Co is regulated and controlled through the tensile stress of Au, and the electronic environment around Pt is further improved, so that the catalytic performance of the catalyst is enhanced; the addition of the carbon nano tube greatly improves the specific surface area of the catalyst and increases the number of active sites. According to experimental data, the Au @ PtCo/CNT catalyst provided by the invention has the advantages of good stability, good hydrogen evolution reaction performance and high hydrogen evolution reaction speed.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
FIG. 1 is a transmission electron micrograph of Au @ PtCo/CNT catalyst prepared in example 1 of the present invention;
FIG. 2 is a graph of the element distribution of the Au @ PtCo/CNT catalyst of example 1 of the present invention;
FIG. 3 is a linear scan element distribution plot of the Au @ PtCo/CNT catalyst prepared in example 1 of the present invention;
FIG. 4 is an X-ray photoelectron spectrum of the Au @ PtCo/CNT catalyst of example 1 of the present invention;
FIG. 5 is an X-ray diffraction pattern of Au @ PtCo/CNT catalyst and multi-walled carbon nanotubes prepared in example 1 of the present invention;
FIG. 6 is a plot of the measured linear sweep voltammograms of the Au @ PtCo/CNT catalyst prepared in example 1 of the present invention and commercial Pt/C;
FIG. 7 is a Tafel slope plot of the Au @ PtCo/CNT catalyst prepared in example 1 and commercial Pt/C calculated by fitting the linear portion of the Tafel plot according to the Tafel equation;
FIG. 8 is a graph of the turnover frequency of the Au @ PtCo/CNT catalyst and commercial Pt/C made in example 1 of the present invention;
FIG. 9 is a graph of the electrochemical impedance of the Au @ PtCo/CNT catalyst and commercial Pt/C made in accordance with example 1 of the present invention;
FIG. 10 is a plot of linear sweep voltammograms before and after cyclic stability testing of the Au @ PtCo/CNT catalyst prepared in example 1 of the present invention and commercial Pt/C;
FIG. 11 is a graph of current versus time for a 10h long term stability test of the Au @ PtCo/CNT catalyst made in accordance with example 1 of the present invention and a commercial Pt/C;
FIG. 12 is a plot of the measured linear sweep voltammogram of the Au @ PtCo/CNT catalyst of example 2 of the present invention;
FIG. 13 is a plot of the measured linear sweep voltammogram of the Au @ PtCo/CNT catalyst of comparative example 1 of the present invention;
FIG. 14 is a plot of the measured linear sweep voltammogram of the Au @ PtCo/CNT catalyst of comparative example 2 of the present invention;
FIG. 15 is a linear sweep voltammogram measured for Au @ PtCo/CNT catalysts prepared in example 1 of the present invention and comparative examples 2-4.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it should be apparent that the embodiments described below are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
This example is the preparation of an Au @ PtCo/CNT catalyst
(1) Weighing a certain amount of Cetyl Trimethyl Ammonium Bromide (CTAB) (0.4mmol) and NaBH4(0.12mmol), L-ascorbic acid (0.15mmol), sodium citrate (0.8mmol), HAuCl4·3H2O(0.053mmol)、CoCl2·6H2O(0.2385mmol)、H2PtCl6·6H2O (0.0795mmol) was prepared as a solution. Then, 20mL of deionized water was added to the 250mL volumetric flask, and 4mL of CTAB at a concentration of 0.1mol/L and 530. mu.L of HAuCl at a concentration of 0.1mol/L were further added4And (4) uniformly mixing the solution. 104.8mg of multi-walled Carbon Nanotubes (CNTs) were added and sonicated for 30 minutes (rate 9000 revolutions per minute). Slowly add 2mL of concentrate dropwise under ice bath (5 deg.C)NaBH degree of 0.06mol/L4And (5) reacting for half an hour.
(2) 3mL of 0.0795mol/L CoCl were added successively2·6H2O and 3mL of H with a concentration of 0.0265mol/L2PtCl6·6H2O solution, 4mL of sodium citrate with a concentration of 0.2mol/L and 5mL of L-ascorbic acid solution with a concentration of 0.03mol/L were added and the mixture was kept at 100 ℃ for 3 hours. Centrifuging at 10000 r/min for 5 min to obtain a product, washing with ethanol and deionized water for three times, and drying in a vacuum drying oven at 35 ℃ overnight to obtain the Au @ PtCo/CNT catalyst.
FIG. 1 is a transmission electron micrograph of the Au @ PtCo/CNT catalyst prepared in this example. As shown in FIG. 1, the strips in FIG. 1 are multi-walled carbon nanotubes, and the particles are Au @ PtCo alloy nanoparticles with a particle size of 10-20 nm. From the figure, it can be seen that the Au @ PtCo alloy nanoparticles are uniformly dispersed on the multi-wall carbon nanotube, and the high dispersibility and small particle size of the nanoparticles can greatly improve the specific surface area and enhance the catalytic performance.
FIG. 2 is a graph showing the element distribution of the Au @ PtCo/CNT catalyst prepared in this example, and FIG. 3 is a graph showing the linear scan element distribution of the Au @ PtCo/CNT catalyst prepared in this example. As can be seen from FIGS. 2 and 3, the Au, Pt and Co elements in the Au @ PtCo/CNT catalyst are uniformly distributed, Au is mainly and intensively distributed in the middle of the Au @ PtCo nanoparticles, and Pt and Co are distributed on the surface layers of the Au @ PtCo nanoparticles, wherein the grain diameter of the core layer is 6-5nm, and the thickness of the shell layer is 7-9 nm.
FIG. 4 is a full spectrum of X-ray photoelectron spectrum of Au @ PtCo/CNT catalyst prepared in this example, and it can be seen that the catalyst contains five elements of Au, Pt, Co, C and O, indicating that the precursor is reduced and the target catalyst is successfully prepared.
FIG. 5 shows the X-ray diffraction patterns of Au @ PtCo/CNT catalyst and multi-walled carbon nanotubes prepared in this example. As can be seen from the figure, the Au @ PtCo/CNT catalyst is good in crystallinity and has no distinct Co characteristic peak, indicating that Co is not formed into nanoparticles, possibly in a monodisperse or monoatomic form. The mass contents of Au, Pt, Co and CNT in the Au @ PtCo/CNT catalyst are respectively 7.48%, 11.22%, 0.16% and 81.14%.
Example 2
This example differs from example 1 in that: by using Co (NO)3)2·6H2Replacement of CoCl by O2·6H2O。
Comparative example 1
This example is the preparation of an Au @ PtCo/CNT catalyst
This example differs from example 1 in that: the reaction temperature in the step (2) is different: the reaction temperature was 80 ℃.
Comparative example 2
This example is the preparation of an Au @ PtCo/CNT catalyst
This comparative example differs from example 1 in that: the amount of carbon nanotubes used was different: the amount of carbon nanotubes used was 209.6 mg.
Comparative example 2
This comparative example differs from example 1 in that: using 0.0265mmol H2PtCl6·6H2O。
Comparative example 3
This comparative example differs from example 1 in that: with 0.053mmol H2PtCl6·6H2O。
Comparative example 4
This comparative example differs from example 1 in that: with 0.106mmol H2PtCl6·6H2O。
Test examples
HER performance was tested using a standard three-electrode system on an electrochemical workstation model CHI-750E and in 1M KOH solution. Graphite rods and Ag/AgCl (3M KCl) electrodes were used as counter and reference electrodes, respectively. The catalyst ink was prepared as follows: first, 5mg of the Au @ PtCo/CNT catalyst prepared in example 1, example 2, comparative example 1 or comparative example 2 and commercial Pt/C were dispersed in 1mL of a mixed solution of isopropyl alcohol, deionized water and 0.5 wt.% of Nafion (isopropyl alcohol: deionized water: Nafion in a volume ratio of 1: 1: 0.1), respectively, and subjected to ultrasonication for 30 minutes to prepare a catalyst ink. Then, 12. mu.L of catalyst ink was dropped onto an L-type glassy carbon electrode (GCE, surface area 0.07 cm) polished with alumina powder2) And naturally drying at room temperature. In a 1M KOH solution first between-0.7V and-1.5V (vs. Ag/AgCl) at 10mV s-1Scanning rate Cyclic Voltammetry (CV) was performed for activation for 6min, followed by Linear Sweep Voltammetry (LSV) measurements. The potential measured for Ag/AgCl was converted to a potential relative to the Reversible Hydrogen Electrode (RHE) according to the equation E (vs. RHE) ═ E (vs. Ag/AgCl) +0.197V +0.059 pH. At 100mV s-1Cyclic voltammetric scan tests were performed for 1000 cycles from-1.2V to-0.9V at the scan rate of (g) to investigate the cyclic stability of the samples.
FIG. 6 is a linear sweep voltammogram measured for the Au @ PtCo/CNT catalyst prepared in example 1 and a commercial Pt/C. As shown in FIG. 6, at a current density of 10mA cm-2When the catalyst is used, the overpotential of the Au @ PtCo/CNT is 14mV, and the commercial Pt/C is 30mV, which shows that the Au @ PtCo/CNT catalyst has obviously better performance than the commercial Pt/C in the alkaline hydrogen evolution reaction.
FIG. 7 is a Tafel slope calculated by fitting the linear portion of the Tafel plot for the Au @ PtCo/CNT catalyst made in example 1 and the commercial Pt/C according to the Tafel equation. The Tafel slope diagram reflects the kinetics of the hydrogen evolution reaction of the catalyst, and it can be seen that the Tafel slope value of Au @ PtCo/CNT is 38.0mV dec-1Specific commercial Pt/C (51.1mV dec)-1) Much lower, indicating a faster hydrogen evolution reaction rate for Au @ PtCo/CNT.
FIG. 8 is a graph of the turnover frequency of the Au @ PtCo/CNT catalyst made in example 1 and commercial Pt/C, the turnover frequency values being used to characterize the activity of each site in the catalyst. The results show that the turnover frequency values of the Au @ PtCo/CNT catalyst are higher than those of the Pt/C catalyst under different potentials, which indicates that the HER kinetics of the Au @ PtCo/CNT catalyst are faster.
FIG. 9 is the electrochemical impedance spectra of the Au @ PtCo/CNT catalyst prepared in example 1 and a commercial Pt/C, from which it can be seen that the charge transfer resistance of the Au @ PtCo/CNT is much lower than that of the commercial Pt/C.
FIG. 10 is a linear sweep voltammogram before and after cyclic stability testing of the Au @ PtCo/CNT catalyst prepared in example 1 and commercial Pt/C. As can be seen from the figure, the Au @ PtCo/CNT catalyst was tested for stability after 1000 cycles at 10mA cm-2The overpotential of commercial Pt/C was shifted by about 13mV, indicating better stability of the Au @ PtCo/CNT catalyst.
FIG. 11 is a graph of the current-time curves of the Au @ PtCo/CNT catalyst prepared in example 1 and the commercial Pt/C after 10h long term stability testing, from which it can be seen that the Au @ PtCo/CNT catalyst is less degraded than the commercial Pt/C, indicating that the Au @ PtCo/CNT catalyst is more stable than the commercial Pt/C.
FIG. 12 is the LSV curve of the Au @ PtCo/CNT catalyst made in example 2, which remains substantially unchanged, illustrating that changing the Co source does not affect the HER performance of the material.
FIG. 13 is a LSV curve of the Au @ PtCo/CNT catalyst prepared in comparative example 1 at a current density of 10mA cm-2When Au @ PtCo/CNT has an overpotential of 40mV, lowering the reaction temperature also lowers the catalyst performance.
FIG. 14 is the LSV curve for the Au @ PtCo/CNT catalyst prepared in comparative example 2 at a current density of 10mA cm-2The overpotential for Au @ PtCo/CNT was 59mV, indicating that increasing the amount of carbon nanotubes decreased HER performance.
FIG. 15 is an LSV curve of Au @ PtCo/CNT catalysts prepared in example 1 and comparative examples 2-4, with different Pt addition levels resulting in catalysts with a volcano-pattern trend in HER performance, with the best performance when the Pt addition level is 0.0795 mmol.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. An Au @ PtCo/CNT catalyst, comprising: a carbon nanotube CNT and an Au @ PtCo alloy supported on the carbon nanotube;
the Au @ PtCo alloy is of a core-shell structure, wherein a shell layer is the PtCo alloy, and a core layer is Au.
2. The Au @ PtCo/CNT catalyst of claim 1, wherein the Au @ PtCo alloy has a particle size of 5 to 40 nm.
3. The Au @ PtCo/CNT catalyst of claim 1, wherein the shell layer has a thickness of 7 to 9nm and the core layer has a particle size of 6 to 5 nm.
4. The Au @ PtCo/CNT catalyst of claim 1, wherein the carbon nanotube CNT is a multi-walled carbon nanotube.
5. The Au @ PtCo/CNT catalyst of claim 1, wherein the Au @ PtCo/CNT catalyst has a mass content of Au, Pt, Co, and CNT of 5-10%, 10-15%, 0.5-1.5%, 70-90%, respectively.
6. A preparation method of an Au @ PtCo/CNT catalyst is characterized by comprising the following steps:
step 1: mixing a gold source solution and a surfactant solution, adding a carbon nano tube for mixing, and adding a first reducing agent for reaction;
step 2: and (2) adding a cobalt source solution and a platinum source solution into the reaction solution obtained in the step (1), and then adding a second reducing agent to react to obtain the Au @ PtCo/CNT catalyst.
7. The method according to claim 6, wherein the gold source is HAuCl4·3H2O、NaAuCl4·2H2O、NaAuCl4·2H2O and Au2Cl6One or more than two of the above;
the cobalt source is CoCl2·6H2O and/or Co (NO)3)2·6H2O；
The platinum source is H2PtCl6·6H2O and/or PtCl4。
8. The production method according to claim 6, wherein the first reducing agent is sodium borohydride;
the second reducing agent is one or more than two of L-ascorbic acid, sodium citrate and ferric chloride;
the surfactant is cetyl trimethyl ammonium bromide and/or cetyl trimethyl ammonium chloride.
9. The production method according to claim 6, wherein the mass ratio of the gold source, the cobalt source, the platinum source, and the carbon nanotube is (1: 5: 3: 7) to (1: 1: 1: 3);
the molar ratio of the surfactant to the gold source is (5: 1) - (10: 1);
the molar ratio of the first reducing agent to the gold source is (1: 1) - (3: 1);
the molar ratio of the second reducing agent to the platinum source is (1: 1) to (3: 1).
10. Use of the Au @ PtCo/CNT catalyst according to any one of claims 1 to 5 or the Au @ PtCo/CNT catalyst prepared by the preparation method according to any one of claims 6 to 9 in a hydrogen evolution reaction.
CN202110657066.8A 2021-06-11 2021-06-11 Au @ PtCo/CNT catalyst and preparation method and application thereof Pending CN113463108A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110586127A (en) * 2019-08-21 2019-12-20 广西大学 Preparation method and application of platinum-cobalt bimetallic hollow nanospheres

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110586127A (en) * 2019-08-21 2019-12-20 广西大学 Preparation method and application of platinum-cobalt bimetallic hollow nanospheres

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
LI-MING GUO: "Structure Design Reveals the Role of Au for ORR Catalytic Performance Optimization in PtCo-Based Catalysts", 《ADV. FUNCT. MATER》 *
NANO RESEARCH: "Facile design of Au@Pt core–shell nanostructures: Formation of Pt submonolayers with tunable coverage and their applications in electrocatalysis", 《NANO RESEARCH》 *

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